Terpene derivatives



Patented June 19, 1945 UNITED STATES PATENT OFFICE TERPENE DERIVATIVESAlfred L. Rummelsburg, Wilmington, Del., assignor to Hercules PowderCompany, Wilmington, Del., a corporation of Delaware No Drawing.Application May 31, 1941, Serial No. 396,217

17 Claims.

This invention relates to a new series of terpene derivatives and tomethods for their production; more particularly, it relates tocondensation products of acyclic terpenes having three double bonds permolecule and a phenol, and to methods for their production.

In accordance with this invention, an acyclic terpene having threedouble bonds per molecule is reacted with a phenol in the presence of anacid catalyst. The resulting product consists primarily of an aromaticether but also contains subferred to employ the particular compound,alloocimene. This acyclic terpene, in addition to having three doublebonds per molecule, has them in a triply conjugated system. Hereinafter,in this specification, an acyclic terpene having three double bonds permolecule will be referred to for convenience merely as an acyclicterpene.

The acyclic terpene employed may be used in any of its monomeric orpolymeric forms. To obtain the polymeric form from the monomer, any ofthe processes known in the art are contemplated. For illustration, inthe case of alloocimene, it is desired to include allo-ocimenepolymerized with phosphoric acid catalysts, such as, orthophosphoricacid, tetraphosphoric acid, hypophosphoric acid, metaphosphoric acid,pyrophosphoric acid, etc., also with metal halide catalysts, such as,stannic chloride, aluminum chloride, zinc chloride, boron trifiuorideand its molecular complexes with ethers and acids, etc. Thepolymerization may be carried out with or without the use of an inert,volatile, organic solvent, such as, benzene, xylene, gasoline, ethylenedichloride, etc. For additional information relating to the particularprocedures which may be employed, see my co-pending applications forUnited States Letters Patent, Serial No. 370,664, filed December 18,1940, and Serial No. 370,665, filed December 18, 1940.

When a polymerized acyclic terpene is employed in the processes ofthisinvention, it is preferable to use a substantially pure dimer. Thisresults from the fact that the increased unsaturation of the acyclicterpene dimer, as compared with that of the higher polymers, facilitatesthe condensation. Thus, when polymerization is carried out with aphosphoric acid catalyst, a liquid product is formed comprising asubstantial quantity of the dimer. In actual practice, the product willcontain from about 75% to about 95% of the dimer, depending upon theconditions of reaction, such as, type of phosphoric acid used, theconcentration of catalyst, the particular solvent, temperatureofreaction, etc. The thiocyanate value of the product may vary from about120 to about 240. If desired, after the catalyst has been removed, thesubstantially pure dimer may be separated from the remainingconstituents using reduced pressure distillation. The substantially puredimer, in the case of allo-ocimene, will be found to have the followingaverage characteristics:

Boiling point (4 mm.) C 142-143 d2 0 8654 n? l. 508

In carrying. out the polymerization with metal halide catalysts, liquidpolymers may also be obtained following the procedure as cited in mycopending application for United States Letters Patent, Serial No.370,664, filed December 18, 1940; however, by employing particular metalhalides and suitably controlling the conditions of the reaction, solidpolymers of acyclic terpenes result. For example, when a metal chloride,and preferably aluminum chloride, is used, generally solid polymersresult. These solid polymers are formed when the reaction is carried outover wide ranges of temperature and using various inert solvents.Preferably, however, to form solid polymers, the reaction is carriedout, at a temperature within the range of from about 35 C. to about C.with the acyclic terpene dissolved in a halogenated organic solvent,such as, ethylene dichloride, etc.

These solid polymers which are prepared by the processes above describedcontain substantial quantities of polymeric constituents higher than thedimer. It has been determined that these organic solids have at leastabout of polymeric constituents higher than the dimer. They are furthercharacterized by having lower thiocyanate values than the liquidpolymers, the values for the former falling within the range of fromabout 20 to about 80.

By employing an acyclic terpene in any of its monomeric or polymericmodifications, as hereinabove described, condensation products may bedric compounds, such as, pyrogallol, hydroxy quinol, phloroglucinol,etc. Polycyclic hydroxyaromatic compounds may be used and thesecompounds may be monoor polyhydric, for example, a-naphthol, p-naphthol,the dihydroxy-naphthalenes, etc. Furthermore, halogen substitutionproducts of the foregoing single and poly ring hydroxy-aromaticcompounds may be employed, for example, ortho-, meta-, andpara-monochlorophenol, the dichlorophenols, the trichlorophenols, thetetrachlorophenols, pentacblorophenol, etc.; also nitrogen substitutionproducts, such as, mononitrophenol, the dinitrophenols, thetrinitrophenols, etc. In addition, monoand polyhydrocarbon substitutionproducts oi. the foregoing monoand polycyclic hydroxy-aromaticcompounds, for example, the cresols, the xylenols, ethyl phenol, propylphenol, butyl phenol, isoamylphenol, etc., may be employed.

In carrying out this invention a condensation catalyst is required forthe reaction. Operable catalysts include the acids, such as, p-toluenesulfonic acid, sulfuric acid, hydrochloric acid,

phosphoric acid, perchloric acid, hydrofluoric acid, fluoboric acid,acetyl sulfuric acid, chloroaluminic acid, etc.; metal halides, such as,aluminum trichloride, stannic chloride, boron trifluoride and itsmolecular complexes-with ethers and organic acids, etc.; also phosphoruspentoxide. Preferably, the amount of catalyst employed should be withinthe range of from about 0.5%

to about 2.0% based on the acyclic terpene or.

polymerized acyclic terpene.

An inert solvent for the reactants may be employed if desired. The useof an inert solvent is particularly advantageous when a solid polymer pfan acyclic terpene is being employed; also when a phenol which is eitherinsoluble or difficultly soluble in the acyclic terpene is beingemployed in the condensation. 'Suitable solvents comprise saturatedpetroleum hydrocarbons, such as, petroleum ether, gasoline, cyclohexane,etc. substituted hydrocarbons, such as carbon tetrachloride, ethylenedichloride, etc.; ethers, such as, ethyl, methyl, isopropyl, etc.;esters, such as, methyl acetate, ethyl acetate, etc.;aromatic-hydrocarbons, such as toluene, xylene, etc.

The condensation reaction inherent in this invention is generallyexothermic. Normally, in carrying out the reaction, the reactants,together with the catalyst, are heated to the reaction temperature ofthe mixture. This temperature may However, it may be desired, after itappears that there is no further reaction taking place as evinced by afall in temperature of the reaction mixture, 'to heat the mixture at atemperature within the range of from about 80 C. to about 200 C. toinsure complete reaction of the constituents. Where amonohydroxy-aromatic compound is employed in the reaction,equi-molecular or other than equi-molecular proportion of the reactantsmay be used. Preferably, the monohydroxy-aromatic compound will beemployed in an amount between a 20% and a 100% excess of equi-molecularproportions. Where a polyhydroxy-aromatic compound is employed,generally less of said polyhydroxy-aromatic compound will be employedthan will be used for a monohydroxy-aromatic compound. For example, inthe case of catechol, a minimum of half a mol is required per mol ofacyclic terpene since two reactive hydroxy groups are present.Theoretically, it is believed that one molecule of acyclic terpene orpolymerized acyclic terpene react with each hydroxyl group present.Thus, the number of hydroxyl groups present in the hydroxy-aromaticcompound employed will determine the theoretical proportion of reactantsto use.

According to the preferred method of carrying out this invention, thephenol and the desired catalyst are first mixed and ,the acyclic terpeneor polymerized acyclic terpene is then slowly added to the admixture.Under these conditions, there is obtained an improved temperaturecontrol, also lighter-colored products result. If the reaction iscarried out inan inert atmosphere, such as, carbon dioxide, nitrogen,hydrogen, etc., additional improvements in color will be obtained.

Following the reaction period, the reaction mixture will be treated toremove the catalyst, any unreacted constituents and the solvent if onehas been employed. If desired, the catalyst may be removed eitherpreceding or following the 'removal of the unreacted constituents andthe solvent which may be present. The catalyst may conveniently beremoved by water washing the product. To accomplish the removal ofunreacted constituents and the solvent which may be present, eithervacuum or steam distillation may be employed.

When metal halides are employed as catalysts, a wash with an aqueoussolution of an inorganic acid, such as, for example, sulfuric acid,hydrochloric acid, phosphoric acid, etc., prior to water washing anddistillation assists in removing traces of metal halide complexes. Inaddition, the presence of traces of many of the catalysts in the productmay be'removed by treatment of the product or its solution in benzene,gasoline, etc., with a suitable adsorbent, such as, activated alumina,fuller's earth, diatomaceous earth, activated carbon, etc., or aselective solvent, such as, furfural, phenol, etc.

The following examples illustrate several speciflc embodiments of theprinciples of the instant invention which, however, are not to beconstrued as being limiting. All parts and percentages are by weightunless otherwise specified.

Example 1 A mixture of 750 parts of monomeric allo-ocimene pure) and 520parts of phenol was heated to 60 C. with 5 parts of p-toluene sulfonicacid at which temperature a vigorous exothermic reaction began. Themixture was cooled with ice to prevent violence and allowed to stand ata temperature of 40 C. for 10 hours, after which it was diluted withbenzol and water washed. The ben- 201 and unreacted constituents wereremoved by reduced pressure distillation to yield 1180 parts 01' aresinous condensate, having a hydroxyl content of 2.4% and a dropmelting point of 35C.

v Example 2 450 parts of phenol were dissolved in 600 parts of monomericallo-ocimene (95% pure).- After adding 2.5 parts of p-toluene sulfonicacid and agitating; a vigorous exothermic reaction began.

. The reaction mixture was allowed to stand overnight in an atmosphereof C02. The product was steam distilled, water washed, and furtherdistilled under reduced pressure to remove unreacted constituents.ahydro'xyl content of 3.0% and a drop melting point of 40 C. remained.

Example 3 To a mixture of 261 parts of monomeric alloocimene (60% pure)with 150 parts of cresol were added 3 parts of p-toluene sulfonic acid.The crude allo-ocimene contained in addition to the allo-ocimene smallquantities of a-pinene, dipentene and unidentified terpenes. The cresolemployed was a mixture of the ortho-, meta-, and

para-modifications. The mixture was allowed to stand for 12 hours at 50C. and then heated to 200 C. under reflux for a period of 1 hour. Theproduct was steam distilled and later washed with water to yield 280parts of a soft resin, having a color of M on the rosin scale, ahydroxyl content of 2.5% and a drop melting point of 45 C.

Example 4 Example 5 To a solution of 700 parts of heat polymerizedallo-ocimene, consisting substantially entirely of the dimer, and 310parts of phenol were added 36 parts of p-toluene sulfonic acid withagitation. An exothermic reaction took place at the completion of whichthe reaction mixture was allowed to cool to 35 C. and then dissolved in5'72 parts of petroleum naphtha. The resulting solution was agitatedwith 20 parts of activated charcoal and filtered. The filtrate wasrapidly washed with 5% NaHCOs solution and the solvent and unreactedconstituents were removed by distillation using a bath temperature of170 C. and a pressure of 3 to 20 mm. 544 parts of condensate remained.It had a hydroxyl content of 2.4% and a drop melting point of 62 C.

Example 6 To a mixture of 142 parts of cresol and 140 parts of liquidpolymerized allo-ocimene, consisting substantially entirely of thedimer, were added 3 parts of p-toluene sulfonic acid with agitation. Anexothermic reaction took place, after which the mixture was heated to200 C. to insure complete reaction. The product was steam distilled toremove unreacted constituents, and water washed to remove the catalyst.197 parts of a dark resinous condensate was obtained. It had a hydroxylcontent of 2.2% and a drop melting point of 58 C.

730 parts of a soft resin which had Example 7 one hundred and forty-fiveparts of u-naphthol and 150 parts of allo-ocimene pure) were mixed andwarmed until'a homogeneous solution resulted. 5 parts of gaseous borontri-fluoride were introduced into the solution at 30 to 50 C.

over a period of 5 minutes with agitation. The

reaction was exothermic. As the evolution of heat subsided, the mixturewas warmed under reflux to C. for two hours, cooled, water washed andthen steam distilled to remove unreactedconstituents. The resultingcondensate was a solid resin, having a'drop melting point of 60 C. andhaving a hydroxyl content of 3.0%.

Example 8 One hundred and forty-five parts of m-naphthol and 300 partsof polymerized allo-ocimene consisting substantially entirely of thedimer were mixed and warmed until a homogeneous solution resulted. 5parts of anhydrous aluminum trichloride were added with agitation.Following the exothermic reaction, the mixture was heated for 3 hours atC., cooled and then washed with aqueous 10% sulfuric acid, then withwater, and later subjected to reduced pressure distillation at 1 mm. andat a bath temperature of 180.

to 240 C. in order to remove unreacted constituents. The resultingcondensate was a solid resin having a drop melting point of 85 C. and ahydroxyl content of 2.0%.

Example 9 One hundred and fifty parts of a crude monochlorinated phenol,comprising substantially en-' have a characteristically high reactivitywith drying oils, such as, linseed, soybean, China-wood,

etc. oils. This is in distinct contrast to the terpene-phenolcondensates previously known in the art. The latter, due to theircomparative low reactivity, cannot be advantageously employed in theproduction of varnishes. The preparation of condensation products byemploying acyclic terpenes, in accordance with this invention,constitutes a solution to this vexatious problem.

The condensation products of this invention may be used as basematerials for the preparation of emulsifying, wetting and sudsingagents. In particular, the sulfonation of these condensates yieldproducts which show the aforesaid characteristics to a marked degree.These condensates may also be reacted with formaldehyde to form hardresins which may be used as such or incorporated in protective coatings.The formaldehyde reaction products, in turn, are reactive with dryingoils; hence, these reaction products may be used in the manufacture ofvarnishes.

It will be understood that in accordance with this invention materialsrich in an acyclic terpene or a polymerized acyclic terpene may beemployed to produce the desired results although a substantially pureacyclic terpene or polymer- 4 ized acyclic terpene is preferred. Animpure allo-ocimene, for example, maybevfcbtained -ig, the pyrolysis ofa-pinene. The-resulting product,

This application constitutes a continuation-in: part of my applicationfor United States Letters Patent, Serial No. 381,854, filed March 5,1941.

What I claim and desire to protect by Letters Patent is:

-1. The process of preparing a new composition of matter which comprisesreacting a mixture of a phenol and a material selected from the groupconsisting of the monomers and polymers of an acyclic terpene having thegeneral formula -CH16, in contact with a catalyst capable of bringingabout a condensation of the mixture, at a reaction temperature of themixture, until condensation is substantially complete.

2. The process of preparing a new composition of matter which comprisesreacting a mixture of a phenol and a material selected from the groupconsisting of the monomers and polymers of an acyclic terpene having thegeneral formula C1oH1s,in contact with an acid catalyst capable ofbringing about a condensation of the mixture, at a reaction temperatureof the mixture, until condensation is substantially complete.

3. The process of preparing a new composition of matter which comprisesreacting a mixture of a phenol and a material selected from the groupconsisting of the monomers and polymers of an acyclic terpene having thegeneral formula C10H1a, in contact with a metal halide catalyst capableof bringing about a condensation of the mixture, at a reactiontemperature .of the mixture, until condensation is substantiallycomplete.

4. The process of preparing a new composition of matter which comprisesreacting a mixture of a phenol and a material selected from the groupconsisting of the monomers and polymers of an acyclic terpene having thegeneral formula CioHm, in contact with p-toluenesulfonic acid, at areaction temperature of the mixture, until condensation is substantiallycomplete.

5. The process of preparing a new composition of matter which comprisesreacting a mixture of a phenol and a material selected from the groupconsisting of the monomers and polymers of an acyclic terpene having thegeneral formula Ciel-I10. in contact with boron trifluoride, at areaction temperature of the mixture, until condensation is substantiallycomplete.

6. The process of preparing a new composition of matter which comprisesreacting a mixture of a phenol and a material selected from the groupconsisting of the monomers and polymers of an acyclic terpene having thegeneral formula Ciel-In, in contact with aluminum chloride, at areaction temperature of the mixture, until condensation is substantiallycomplete.

7. The process of preparing a new composition of matter which comprisesreacting a mixture of a phenol and an acyclic terpene hydrocarbon havingthe general formula CroHm, in contact with ptoluenesulfonic acid, at areaction temperature of the mixture, until condensation is substantiallycomplete.

8. The process of preparing a new composition of matter which comprisesreacting a mixture of phenol and allo-ocimene in contact withptoluenesulfonic acid, at a reaction temperature of the mixture, untilcondensation is substantially complete,

9. The process of preparing a new composition of matter which comprisesreacting a mixture of a phenol and polymers of an acyclic terpene havingthe general formula CmHia. in contact with boron trifluoride, at areaction temperature of the mixture, until condensation is substantiallycomplete.

19. The process of preparing a new composition of matter which comprisesreacting a mixture of phenol and polymerized allo-ocimene in contactwith boron trifluoride, at a reaction temperature of the mixture, untilcondensation is substantially complete.

11. The product produced in accordance with the process of claim 1.

12. The product produced in accordance with the process of claim 1 butwhere thematerial is allo-ocimene.

13. The product produced in accordance with the process of claim 1 butwhere the material is myrcene.

14. The product produced in accordance with the process of claim 1 butwhere the material is polymerized allo-ocimene.

15. The product produced in accordance with the process of claim 1 butwhere the material is dimeric allo-ocimene.

16. The product produced in accordance with the process of claim 8.

17. The product produced in accordance with the process of claim 10.

ALFRED L. RUMMELSBURG.

